Aqueous water-and oil-repellent dispersion

ABSTRACT

An aqueous water- and oil-repellent dispersion containing: (A) a homopolymer or copolymer containing at least one polymerizable compound having a perfluoroalkyl or perfluoroalkenyl group and an acrylate or methacrylate group, or a copolymer containing said polymerizable compound and another compound copolymerizable therewith, (B) an organic solvent which is tripropylene glycol, and (C) a surfactant, has durable water- and oil-repellency and excellent storage stability.

FIELD OF THE INVENTION

The present invention relates to an aqueous water- and oil-repellentdispersion comprising a polymer containing a polymerizable compoundhaving a perfluoroalkyl or perfluoroalkenyl group and an acrylate ormethacrylate group, which can impart the water- and oil repellency tovarious fibers.

RELATED ARTS

It is well known that a polymer of a polymerizable compound having aperfluoroalkyl or perfluoroalkenyl group and an acrylate or methacrylategroup can be used as a water- and oil-repellent for a fibrous fabric. Anaqueous dispersion which is prepared by dispersing the polymer in anaqueous medium by means of an emulsifier widely has the industrialutilization. However, the water- and oil-repellency of a fibrous fabrictreated with usual conventional aqueous dispersions is not satisfactoryfor resistance, namely durability, to physical action such as friction.In addition, the conventional aqueous dispersions do not have excellentstorage stability even if they have the durable water- and oilrepellency.

SUMMARY OF THE INVENTION

One of the objects of the present invention is to provide an aqueouswater- and oil-repellent dispersion having durable water- andoil-repellency and excellent storage stability.

The present invention provides an aqueous water- and oil-repellentdispersion comprising:

(A) a homopolymer or copolymer comprising at least one polymerizablecompound having a perfluoroalkyl or perfluoroalkenyl group and anacrylate or methacrylate group, or

a copolymer comprising said polymerizable compound and another compoundcopolymerizable therewith,

(B) an organic solvent which is tripropylene glycol, and

(C) a surfactant.

DETAILED EXPLANATION OF THE INVENTION

In the copolymer, which is the polymer (A), comprising the polymerizablecompound having the perfluoroalkyl or perfluoroalkenyl group and theacrylate or methacrylate group and the another compound copolymerizabletherewith, the former compound is in the amount of at least 25% byweight, preferably at least 40% by weight based on the weight of thecopolymer.

Examples of the polymerizable compound having the perfluoroalkyl orperfluoroalkenyl group and the acrylate or methacrylate group include(meth)acrylate esters represented by the formulas:

wherein Rf is a perfluoroalkyl or perfluoroalkenyl group having 3 to 21carbon atoms,

R¹ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms,

R² is an alkylene group having 1 to 10 carbon atoms,

R³ is a hydrogen atom or a methyl group,

Ar is an aryl group which optionally has a substituent group, and

n is an integer of 1 to 10.

Specific examples of the polymerizable compound include:

CF₃(CF₂)₇(CH₂)OCOCH═CH₂,

CF₃(CF₂)₆(CH₂)OCOC(CH₃)═CH₂,

(CF₃)₂CF(CF₂)₆(CH₃)₂OCOCH═CH₂,

CF₃(CF₂)₇(CH₂)₂OCOC(CH₃)═CH₂,

CF₃(CF₂)₇(CH₂)₂OCOCH═CH₂,

CF₃(CF₂)₇SO₂N(CH₃)(CH₂)₂OCOCH═CH₂,

CF₃(CF₂)₇SO₂N(C₂H₅)(CH₂)₂OCOC(CH₃)═CH₂,

(CF₃)₂CF(CF₂)₆CH₂CH(OCOCH₃)CH₂OCOC(CH₃)═CH₂,

(CF₃)₂CF(CF₂)₆CH₂CH(OH)CH₂OCOCH═CH₂,

The another copolymerizable compound are various. Examples of theanother copolymerizable compound include: (1) acrylic acid andmethacrylic acid, and methyl, ethyl, butyl, isobutyl, t-butyl, propyl,2-ethylhexyl, hexyl, decyl, lauryl, stearyl, isobornyl, P-hydroxyethyl,glycidyl, phenyl, benzyl and 4-cyanophenyl esters thereof; (2) vinylesters of fatty acids such as acetic acid, propionic acid, caprylicacid, lauric acid and stearic acid; (3) styrene compounds such asstyrene, a-methylstyrene and p-methylstyrene; (4) vinyl halides andvinylidene compounds such as vinyl fluoride, vinyl chloride, vinylbromide, vinylidene fluoride and vinylidene chloride; (5) fatty acidallyl esters such as allyl heptanoate, allyl caprylate and allylcaproate; (6) vinyl alkyl ketones such as vinyl methyl ketone and vinylethyl ketone; (7) acryl amides such as N-methylacrylamide andN-methylolmethacrylamide; and (8) dienes such as2,3-dichloro-1,3-butadiene and isoprene.

The organic solvent in the present invention is tripropylene glycol,H[OCH₂CH(CH₃)]₃OH.

The amount of the organic solvent (B) may be from 5 to 200 parts byweight, for example from 10 to 100 parts by weight, particularly from 20to 60 parts by weight, based on 100 parts of the polymer (A).

The surfactant (C) used for dispersing the polymer and the organicsolvent may be a cationic emulsifier, an anionic emulsifier or anonionic emulsifier. The surfactant is preferably the cationicemulsifier, the nonionic emulsifier or a mixture of both. In the case ofthe mixture, a preferable weight ratio of the cationic emulsifier to thenonionic emulsifier is from 1:9 to 9:1. Specific examples of thecationic emulsifier include dodecyl trimethyl ammonium acetate,trimethyl tetradecyl ammonium chloride, hexadecyl trimethyl ammoniumbromide, trimethyl octadecyl ammonium chloride, (dodecylmethyl-benzyl)trimethyl ammonium chloride, benzyl dedecyl dimethyl ammonium chloride,methyl dodecyl di(hydropolyoxy-ethylene) ammonium chloride, benzyldodecyl di(hydropoly-oxyethylene) ammonium chloride, benzyl dodecyldi(hydro-polyoxyethylene) ammonium chloride andN-[2-(diethyl-amino)ethyl]oleamide hydrochloride. Specific examples ofthe nonionic emulsifier include a condensation product of ethylene oxidewith hexyl phenol, iso-octyl phenol, hexadecanol, oleic acid,alkane(C₁₂-C₁₆)thiol, sorbitan monofatty acid (C₇-C₁₉) oralkyl(C₁₂-C₁₈)amine and the like.

The amount of the surfactant (C) may be from 0.01 to 30 parts by weight,for example from 1 to 20 parts by weight, based on 100 parts by weightof the polymer (A).

The dispersion according to the present invention can be prepared byemulsion-polymerizing the polymerizable compound(s) in water accompaniedby the organic solvent (B) in the presence of the surfactant to give anemulsion of the polymer (A). Water and/or the surfactant may be added tothe emulsion of the polymer (A).

Examples of a suitable substrate, to which the dispersion according tothe present invention is applied, include a film, a fiber, a yarn, awoven fabric, a carpet, a filament made from a natural polymer material,a modified natural polymer material and a synthetic polymer material,and a product made from a fiber and a yarn. The substrate is preferablya textile which is in the form of a fiber, a yarn or a fabric.

The dispersion according to the present invention can be applied to thesubstrate preferably by coating, dipping, spraying, padding, rollcoating, or combination of these procedures. For example, a padding bathhaving the bath solid content of 0.1 to 10% by weight can be used. Thesubstrate is padded in the bath, and then excess liquid is usuallyremoved by a squeezing roll to give the dry pickup amount (the weight ofdry polymer on the substrate) of from 0.01 to 10% by weight based on theweight of the substrate. Then, the treated substrate is preferablyheated at 100-200° C.

PREFERRED EMBODIMENTS OF THE INVENTION

Examples and Comparative Examples are shown hereinafter to illustratethe present invention in detail.

Properties are determined as follows:

Water- and Oil-repellency

The polymer dispersion liquid is diluted with water to give a treatmentliquid having a solid content of 0.08% by weight. A polyester fabric isimmersed in the treatment liquid, squeezed with a mangle to give a wetpickup of 65%, dried at 100° C. for two minutes, heated at 160° C. forone hour, and then subjected to an evaluation of water- andoil-repellency.

The water-repellency is expressed by the water repellency No. (cf. thefollowing Table 1) determined by the spray method according to JIS(Japanese Industrial Standard) L-1092.

The oil-repellency is determined by dropping several drops of a testsolution shown in AATCC-TM118 (Table 2) on two positions of a surface ofa test cloth and observing the penetration state of the drops after 30seconds. The maximum point at which the test solution exhibits nopenetration is expressed by the oil-repellency.

TABLE 1 Water repellency No. State 5 No wet on the surface 4 Slight weton the surface 3 Partial wet on the surface 2 Wet on the surface 1 Wetover the whole surface

TABLE 2 Surface tension Oil (dyne/cm, repellency Test solution 25° C.) 8n-Heptane 20.0 7 n-Octane 21.8 6 n-Decane 23.5 5 n-Dodecane 25.0 4n-Tetradecane 26.7 3 n-Hexadecane 27.3 2 n-Hexadecane/Nujol mixturesolution 29.6 (35/65 by weight) 1 Nujol 31.2 0 Inferior to 1 —

Storage stability

After the aqueous dispersion (solid content: 30% by weight) is stored at40° C. for one month, the generation of precipitation is observed.

∘: No precipitation

Δ: Slight precipitation

×: Much precipitation

EXAMPLE 1

100 g of C_(n)F_(2n+1)CH₂CH₂OCOCH═CH₂ (a mixture of compounds wherein nis 6, 8, 10, 12 and 14 (average of n is 8)), 50 g of stearyl acrylate, 2g of N-methylol acrylamide, 200 g of pure water, 40 g of tripropyleneglycol, 0.3 g of acetic acid, 4 g of alkyl trimethyl ammonium chlorideand 10 g of polyoxyethylenealkylphenyl ether were charged into a 500 mLflask and emulsified at 60° C. for 15 minutes by means of ultrasonicwave with stirring. 0.75 g of azobisisobutylamidine dihydrochloride wasadded and the reaction was continued for 5 hours to give an aqueousdispersion of a polymer.

The water- and oil-repellency and the storage stability were evaluated.The results are shown in Table 3.

EXAMPLE 2

100 g of C_(n)F_(2n+1)CH₂CH₂OCOCH═CH₂ (a mixture of compounds wherein nis 6, 8, 10, 12 and 14 (average of n is 8)), 50 g of stearyl acrylate, 2g of 3-chloro-2-hydroxypropyl methacrylate, 200 g of pure water, 30 g oftripropylene glycol, 0.3 g of acetic acid, 4 g of alkyl trimethylammonium chloride and 10 g of polyoxyethylenealkylphenyl ether werecharged into a 500 mL flask and emulsified at 60° C. for 15 minutes bymeans of ultrasonic wave with stirring. 0.75 g of azobisisobutylamidinedihydrochloride was added and the reaction was continued for 5 hours togive an aqueous dispersion of a polymer.

The water- and oil-repellency and the storage stability were evaluated.The results are shown in Table 3.

EXAMPLE 3

100 g of C_(n)F_(2n+1)CH₂CH₂OCOCH═CH₂ (a mixture of compounds wherein nis 6, 8, 10, 12 and 14 (average of n is 8)), 25 g of stearyl acrylate,25 g of 2-ethylhexyl methacrylate, 200 g of pure water, 80 g oftripropylene glycol, 0.3 g of acetic acid, 4 g of alkyl trimethylammonium chloride and 10 g of polyoxyethylenealkyl ether were chargedinto a 500 mL flask and emulsified at 60° C. for 15 minutes by means ofultrasonic wave with stirring. 0.75 g of azobisisobutyl-amidinedihydrochloride was added and the reaction was continued for 5 hours togive an aqueous dispersion of a polymer.

The water- and oil-repellency and the storage stability were evaluated.The results are shown in Table 3.

EXAMPLE 4

100 g of C_(n)F_(2n+1)CH₂CH₂OCOCH═CH₂ (a mixture of compounds wherein nis 6, 8, 10, 12 and 14 (average of n is 8)), 50 g of stearyl acrylate, 2g of diacetone acrylamide, 200 g of pure water, 50 g of tripropyleneglycol, 0.3 g of acetic acid, 4 g of alkyl trimethyl ammonium chlorideand 10 g of polyoxyethylenealkylphenyl ether were charged into a 500 mLflask and emulsified at 60° C. for 15 minutes by means of ultrasonicwave with stirring. 0.75 g of azobisisobutyl-amidine dihydrochloride wasadded and the reaction was continued for 5 hours to give an aqueousdispersion of a polymer.

The water- and oil-repellency and the storage stability were evaluated.The results are shown in Table 3.

EXAMPLE 5

100 g of C_(n)F_(2n+1)CH₂CH₂OCOCH═CH₂ (a mixture of compounds wherein nis 6, 6, 10, 12 and 14 (average of n is 8)), 25 g of stearyl acrylate,25 g of 2-ethylhexyl methacrylate, 2 g of N-methylolacrylamide, 200 g ofpure water, 60 g of tripropylene glycol, 0.3 g of acetic acid, 4 g ofalkyl trimethyl ammonium chloride and 10 g of polyoxyethylene-alkylether were charged into a 500 mLL flask and emulsified at 60° C. for 15minutes by means of ultrasonic wave with stirring. 0.75 g ofazobisisobutylamidine dihydrochloride was added and the reaction wascontinued for 5 hours to give an aqueous dispersion of a polymer.

The water- and oil-repellency and the storage stability were evaluated.The results are shown in Table 3.

Comparative Example 1

The procedure of Example 1 was repeated except that 40 g of propyleneglycol was used instead of 40 g of tripropylene glycol.

Comparative Example 2

The procedure of Example 1 was repeated except that 40 g of dipropyleneglycol was used instead of 40 g of tripropylene glycol.

Comparative Example 3

The procedure of Example 2 was repeated except that 30 g of propyleneglycol was used instead of 30 g of tripropylene glycol.

Comparative Example 4

The procedure of Example 2 was repeated except that 30 g of dipropyleneglycol was used instead of 30 g of tripropylene glycol.

Comparative Example 5

The procedure of Example 4 was repeated except that 50 g of propyleneglycol was used instead of 50 g of tripropylene glycol.

TABLE 3 Water- and oil repellency Durability Initial HL-3 DC-3 Water-Oil- Water- Water- Water- Water- Storage repellency repellencyrepellency repellency repellency repellency stability Ex. 1 5 6 4 4 4 3∘ Ex. 2 5 6 4 4 4 3 ∘ Ex. 3 5 7 4 5 4 4 ∘ Ex. 4 5 6 4 4 4 3 ∘ Ex. 5 5 74 5 4 4 ∘ Com. 5 6 4 4 4 3 x Ex. 1 Com. 5 6 4 4 4 3 Δ Ex. 2 Com. 5 6 4 44 3 x Ex. 3 Com. 5 6 4 4 4 3 x Ex. 4 Com. 5 6 4 4 4 3 x Ex. 5 Note)HL-3: After 3 times washing according to a JIS L-0217-103 method DC-3:After 3 times dry cleaning according to a JIS L-1092-322 method

EFFECTS OF THE INVENTION

Tripropylene glycol used in the present invention is excellent in noharm. The aqueous dispersion according to the present invention iseffective for decreasing the environmental pollution and has durablewater- and oil-repellency and excellent storage stability.

What is claimed is:
 1. An aqueous water- and oil-repellent dispersioncomprising: (A) a homopolymer or copolymer comprising at least onepolymerizable compound having a perfluoroalkyl or perfluoroalkenyl groupand an acrylate or methacrylate group, or a copolymer comprising saidpolymerizable compound and another compound copolymerizable therewith,(B) an organic solvent which is tripropylene glycol, and (C) asurfactant, wherein the amount of the organic solvent (B) is from 5 to200 parts by weight, based on 100 parts by weight of the polymer (A),and a polymer in the dispersion consists essentially of the polymer (A)prepared by emulsion-polymerizing the polymerizable compound in wateraccompanied by the organic solvent (B).
 2. The dispersion according toclaim 1, wherein the amount of the organic solvent (B) is from 10 to 100parts by weight, based on 100 parts by weight of the polymer (A).
 3. Atextile, to which the dispersion according to claim 1 is applied.
 4. Amethod of producing the aqueous water- and oil-repellent dispersionaccording to claim 1, comprising steps of: emulsion-polymerizing atleast one polymerizable compound having a perfluoroalkyl orperfluoroalkenyl group and an acrylate or methacrylate group in wateraccompanied by an organic solvent which is tripropylene glycol to givean emulsion of a polymer of the polymerizable compound.
 5. Thedispersion according to claim 1, wherein the amount of the organicsolvent (B) is from 20 to 60 parts by weight, based on 100 parts byweight of the polymer (A).
 6. The dispersion according to claim 1,wherein the surfactant (C) is a cationic emulsifier, a nonionicemulsifier or a mixture of a cationic emulsifier and a nonionicemulsifier.
 7. The dispersion according to claim 1, wherein the amountof the surfactant (C) is from 0.01 to 30 parts by weight, based on 100parts by weight of the polymer (A).
 8. The dispersion according to claim7, wherein the amount of the surfactant (C) is from 1 to 20 parts byweight, based on 100 parts by weight of the polymer (A).